U.S. patent number 5,929,289 [Application Number 09/033,633] was granted by the patent office on 1999-07-27 for stabilization of phosphite ligands in hydroformylation process.
This patent grant is currently assigned to Union Carbide Chemicals & Plastics Technology Corporation. Invention is credited to Anthony George Abatjoglou, David Robert Bryant, John Michael Maher.
United States Patent |
5,929,289 |
Abatjoglou , et al. |
July 27, 1999 |
Stabilization of phosphite ligands in hydroformylation process
Abstract
The present invention provides a hydroformylation process
comprising: (1) forming a reaction mixture containing: (a) an
olefinic compound, (b) hydrogen, (c) carbon monoxide, (d) a
phosphite in which each phosphorus atom is bonded to three oxygen
atoms and at least one such oxygen atom is bonded to a carbon atom
of an aromatic ring that is adjacent to another carbon atom of said
ring having a pendant monovalent group having a steric hindrance at
least as great as the steric hindrance of the isopropyl group, (e)
a catalytic amount of rhodium, and (f) a Group VIII metal (other
than a rhodium) in an amount sufficient to reduce the
rhodium-catalyzed decomposition of the phosphite during the
hydroformylation process; and (2) maintaining the reaction mixture
under conditions at which the olefinic compound reacts with the
hydrogen and carbon monoxide to form an aldehyde.
Inventors: |
Abatjoglou; Anthony George
(Charleston, WV), Bryant; David Robert (South Charleston,
WV), Maher; John Michael (Charleston, WV) |
Assignee: |
Union Carbide Chemicals &
Plastics Technology Corporation (Danbury, CT)
|
Family
ID: |
23127321 |
Appl.
No.: |
09/033,633 |
Filed: |
March 3, 1998 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
Issue Date |
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293028 |
Aug 19, 1994 |
5756855 |
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Current U.S.
Class: |
568/454; 502/158;
502/167; 568/451; 502/161; 502/166 |
Current CPC
Class: |
C07C
45/50 (20130101); B01J 31/185 (20130101); C07C
45/50 (20130101); C07C 47/02 (20130101); B01J
2231/321 (20130101); B01J 2531/80 (20130101); B01J
2531/824 (20130101); B01J 2531/0288 (20130101); B01J
2531/821 (20130101); B01J 2531/845 (20130101) |
Current International
Class: |
B01J
31/18 (20060101); B01J 31/16 (20060101); C07C
45/50 (20060101); C07C 45/00 (20060101); C07C
045/50 (); B01J 031/20 () |
Field of
Search: |
;568/454,451
;502/158,161,166,167 |
References Cited
[Referenced By]
U.S. Patent Documents
Foreign Patent Documents
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0518241 |
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Jun 1991 |
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EP |
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0590611 |
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Apr 1994 |
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EP |
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348284 |
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Nov 1956 |
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CH |
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Other References
Anna M. Trzeciak et al., Synthesis and Properties of the
Orthometallated Rhodium Complex Rh {P(OPh).sub.3 }.sub.3
{P(OC.sub.6 H.sub.4)(OPh).sub.2 } Z. anorg. allg. Chem. 577 (1989),
pp. 255-262. .
F.H. Westheimer, et al., Rates and Mechanisms of Hydrolysis of
Esters of Phosphorous Acid, J. Am. Chem Soc. 1988, 110,pp. 181-185.
.
L.N. Lewis et al, Catalytic C-C Bond Formation via Ortho-Metalated
Complexes, J. Am. Chem. Soc., vol. 108, No. 10, 1986, 1986, pp.
2728-2735..
|
Primary Examiner: Kumar; Shailendra
Assistant Examiner: Padmanabhan; Sreeni
Attorney, Agent or Firm: Coon; Gerald L.
Parent Case Text
This application is a divisional application of application Ser.
No. 08/293,028 filed Aug. 19, 1994 now U.S. Pat. No. 5,756,855.
Claims
What is claimed is:
1. A hydroformylation catalyst precursor composition comprising:
(i) a rhodium catalyst precursor, (ii) a precursor compound of a
Group VIII metal (other than a rhodium compound) in an amount that
provides a sufficient amount of the Group VIII metal to reduce the
rhodium-catalyzed decomposition of the phosphite described in (iii)
below during hydroformylation and (iii) a phosphite in which each
phosphorus atom is bonded to three oxygen atoms and at least one
such oxygen atom is bonded to a carbon atom of an aromatic ring
that is adjacent to another carbon atom of said ring having a
pendant monovalent group having a steric hindrance at least as
great as the steric hindrance of the isopropyl group.
2. A hydroformylation catalyst composition comprising: (i) rhodium
in complex combination with carbon monoxide and a phosphite in
which each phosphorus atom is bonded to three oxygen atoms and at
least one such oxygen atom is bonded to a carbon atom of an
aromatic ring that is adjacent to another carbon atom of said ring
having a pendant monovalent group having a steric hindrance at
least as great as the steric hindrance of the isopropyl group, and
(ii) a Group VIII metal (other than a rhodium compound) in complex
combination with carbon monoxide and said phosphite, said Group
VIII metal being present in an amount sufficient to reduce
rhodium-catalyzed decomposition of the phosphite during
hydroformylation.
Description
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to a process wherein certain metals
are used in hydroformylation reaction mixtures containing phosphite
ligands susceptible to rhodium-catalyzed degradation in order to
stabilize the ligands against such degradation.
2. Description of Related Art
It is known to produce aldehydes by hydroformylating reaction
mixtures comprising an olefinic compound, hydrogen, carbon
monoxide, rhodium and a phosphite ligand. Complex catalysts formed
in situ from the rhodium, ligand and carbon monoxide catalyze such
hydroformylation reactions. Such processes are disclosed, for
example in U.S. Pat. No. 4,599,206 which relates to the use of
specific class of phosphite ligands (referred to therein as
"diorganophosphite" ligands) in hydroformylation.
Such known hydroformylation processes suffer from the drawback that
certain phosphite ligands are susceptible to rhodium-catalyzed
decomposition which results not only in a loss of the expensive
ligands but which may also result in deactivation of the rhodium by
the ligand decomposition products. An example of one type of
rhodium-catalyzed phosphite degradation is disclosed in "Synthesis
and Properties of the Orthometallated Rhodium Complex
Rh{P(OPh).sub.3 }.sub.3 {P(OC.sub.6 H.sub.4)(OPh).sub.2 }", Anna M.
Trzeciak and Josef J. Ziolkowski, Z. Anorg. Allg. Chem. 577,
(1989), 255-262.
Rhodium-catalyzed phosphite degradation is distinct from
acid-catalyzed hydrolytic phosphite degradation disclosed, for
example, in "Rates and Mechanisms of Hydrolysis of Esters of
Phosphorous Acid", F. H. Westheimer, Shaw Huang, and Frank Covitz,
J. Am. Chem. Soc., 1988, 110, 181-185. Phosphites sensitive to one
of these forms of degradation may be relatively insensitive to the
other form of degradation and stabilizers against one form of
phosphite degradation do not necessarily stabilize against the
other form of phosphite degradation. For example, published
European Patent Application 0590611 discloses that epoxides
stabilize phosphites against acid-catalyzed hydrolytic degradation
in hydroformylation reaction mixtures but epoxides do not stabilize
phosphites against rhodium-catalyzed degradation.
It is an object of the present invention to provide a
hydroformylation process using phosphite ligands that are
susceptible to, but are stabilized against, rhodium-catalyzed
degradation.
Other objects of the present invention will be apparent from the
description thereof appearing below.
SUMMARY OF THE INVENTION
The present invention provides hydroformylation process comprising:
(1) forming a reaction mixture containing: (a) an olefinic
compound, (b) hydrogen, (c) carbon monoxide, (d) a phosphite in
which each phosphorus atom is bonded to three oxygen atoms and at
least one such oxygen atom is bonded to a carbon atom of an
aromatic ring that is adjacent to another carbon atom of said ring
having a pendant monovalent group having a steric hindrance at
least as great as the steric hindrance of the isopropyl group, (e)
a catalytic amount of rhodium, and (f) a Group VIII metal (other
than rhodium) in an amount sufficient to reduce the
rhodium-catalyzed decomposition of the phosphite during the
hydroformylation process; and (2) maintaining the reaction mixture
under conditions at which the olefinic compound reacts with the
hydrogen and carbon monoxide to form an aldehyde.
The present invention also provides a hydroformylation catalyst
precursor composition comprising: (i) a rhodium catalyst precursor,
(ii) a compound of a Group VIII metal (other than a rhodium
compound) in an amount that provides a sufficient amount of the
Group VIII metal to reduce the rhodium-catalyzed decomposition of
the phosphite described in (iii) below during hydroformylation and
(iii) a phosphite in which each phosphorus atom is bonded to three
oxygen atoms and at least one such oxygen atom is bonded to a
carbon atom of an aromatic ring that is adjacent to another carbon
atom of said ring having a pendant monovalent group having a steric
hindrance at least as great as the steric hindrance of the
isopropyl group.
The present invention further provides a hydroformylation catalyst
composition comprising: (i) rhodium in complex combination with
carbon monoxide and a phosphite in which each phosphorus atom is
bonded to three oxygen atoms and at least one such oxygen atom is
bonded to a carbon atom of an aromatic ring that is adjacent to
another carbon atom of said ring having a pendant monovalent group
having a steric hindrance at least as great as the steric hindrance
of the isopropyl group, and (ii) a Group VIII metal (other than a
rhodium compound) in complex combination with carbon monoxide and
said phosphite, said Group VIII metal being present in an amount
sufficient to reduce the rhodium-catalyzed decomposition of the
phosphite during hydroformylation.
DETAILED DESCRIPTION OF THE INVENTION
The reaction mixtures used in the process of the present invention
contain rhodium. The rhodium functions as a hydroformylation
catalyst in the form of a complex comprising the rhodium complexed
with carbon monoxide and the phosphite ligand. When used herein to
describe such complex catalysts, the term "comprising" is not meant
to exclude, but rather includes, other ligands (e.g., hydrogen or
other organic ligands, such as the olefin reactant) also complexed
with the rhodium. However, the term "comprising" is meant to
exclude materials in amounts which unduly poison or deactivate the
catalyst. Thus, the catalyst is desirably free of significant
amounts of contaminants such as rhodium-bound halogen (e.g.,
chlorine) and the like.
The complex catalysts involved in the process of the present
invention may be formed by methods known in the art. For instance,
preformed rhodium hydridocarbonyl (mono-phosphite) complexes may be
prepared and introduced into the reaction mixture used in the
hydroformylation process. Preferably, the catalysts used in this
invention can be derived from a metal catalyst "precursor" which is
introduced into the reaction mixture for in situ formation of the
active catalyst complex in the reaction mixture. For example,
rhodium catalyst precursors (such as rhodium dicarbonyl
acetylacetonate, Rh.sub.2 O.sub.3, Rh.sub.4 (CO).sub.12, Rh.sub.6
(CO).sub.16, Rh(NO.sub.3).sub.3, rhodium acetylacetonate, and the
like) may be introduced into the reaction mixture and the active
catalyst complex can be formed in the reaction mixture by the
precursor complexing with separately-added phosphite ligand and
carbon monoxide. As a further example, in a preferred embodiment of
the present invention, rhodium dicarbonyl acetylacetonate is
reacted with a phosphite in presence of a solvent to form a rhodium
carbonyl diorganophosphite acetylacetonate precursor. The precursor
so formed is introduced into the hydroformylation reactor along
with excess free phosphite ligand for the in situ formation of an
active catalyst in the reactor by complexing with carbon monoxide
in the reactor. In any event, it is sufficient for the purpose of
this invention to understand that carbon monoxide and phosphites
are ligands that are capable of being complexed with the rhodium
(along with other ligands such as hydrogen and a portion of the
olefin reactant) and that an active rhodium catalyst complex is
present in the reaction mixture under the conditions of the
hydroformylation process.
The phosphite ligands useful in the process of the present
invention contain one or more trivalent phosphorus atoms and each
valence of the phosphorus atom bonds the phosphorus atom to a
carbon atom of an aromatic ring through an oxygen atom and that
carbon atom of at least one of the aromatic rings is adjacent to
another carbon atom of the aromatic ring to which is bonded a
pendant monovalent group (hereinafter called "hindering group")
having a steric hindrance at least as great as the steric hindrance
of the isopropyl group. Illustrative of such blocking groups are
branched alkyl groups containing at least 3 carbon atoms such as
the isopropyl, secondary butyl, tertiary butyl, secondary amyl and
tertiary amyl groups; cycloalkyl groups such as the cyclohexyl
group; alkaryl groups such as the tolyl group; aralkyl groups such
as the benzyl group and aryl groups such as the phenyl group.
Phosphite ligands containing such hindering groups undergo
rhodium-catalyzed degradation during hydroformylation in the
absence of a Group VIII metal stabilizer. The Group VIII metal
stabilizer reduces the decomposition of the phosphite by at least
five percent by weight. For example, in the absence of a Group VIII
metal stabilizer, at least about fifty weight percent of such
phosphite ligands will decompose in rhodium-catalyzed
hydroformylation process over a twelve day reaction period under
the conditions used in Example 1 below. By way of comparison, under
the conditions used in Example 1 below, less than about forty
weight percent of such phosphite ligands will decompose in the
presence of a Group VIII in accordance with the process of the
present invention.
Suitable phosphite ligands useful in the process of the present
invention include:
A. diorganophosphites having the formula: ##STR1## (1) Ar
represents an aryl group, at least one of which aryl groups having
a pendant hindering group ortho to the carbon atom to which the
oxygen atom is attached;
(2) y has a value of 0 or 1;
(3) Q represents a divalent bridging group selected from the class
consisting of --CR.sup.1 R.sup.2 --, --O--, --S--, --NR.sub.3 --,
--SiR.sup.4 R.sup.5 --, and --CO--;
(4) R.sup.1 and R.sup.2 each represent a group selected from the
group consisting of hydrogen, an alkyl group containing 1 to 12
carbon atoms and the phenyl, tolyl and anisyl groups;
(5) R.sup.3, R.sup.4, and R.sup.5 each represent hydrogen or an
alkyl group;
(6) n has a value of 0 to 1; and
(7) T represents a monovalent hydrocarbon group;
B. partially open ended bis-phosphites having the formula: ##STR2##
wherein D represents a divalent bridging group selected from the
group consisting of alkylene, alkylene-oxy-alkylene, arylene, and
arylene (CH.sub.2).sub.y --Q.sub.n --(CH.sub.2).sub.y -arylene and
wherein Ar, Q, n, y and T are as defined for formula (I) above;
C. triorganophosphites having the formula:
wherein R.sup.o is a substituted or unsubstituted monovalent
aromatic group, at least one of which aromatic groups group has a
pendant hindering group ortho to the carbon atom to which the
oxygen atom is attached;
D. phosphites having the formula:
wherein R.sup.a, R.sup.b and R.sup.c each an represent aryl group,
at least one of which aromatic groups group has a pendant hindering
group ortho to the carbon atom to which the oxygen atom is
attached, provided that at least one of R.sup.a, R.sup.b and
R.sup.c represents a group having the formula: ##STR3## wherein Q
represents a group having the formula: ##STR4## or a group having
the formula: ##STR5## wherein each R.sup.e represents an optionally
fluorine-containing hydrocarbyl group, R.sup.f represents a
hydrogen atom or an R.sup.e group and R.sup.d represents a hydrogen
atom or an inert (to the hydroformylation reaction) substituent on
the meta and/or para position of the ring, X represents an oxygen
or sulphur atom, n is 0 or 1 and R.sup.g represents a hydrogen atom
or an inert (to the hydroformylation reaction) substituent of the
ring;
E. polyphosphite ligands having the general formula: ##STR6##
wherein each Ar group represents an identical or different aryl
group, at least one of which aryl groups having a pendant hindering
group ortho to the carbon atom to which the oxygen atom is
attached; wherein X represents a m-valent radical selected from the
group consisting of alkylene, alkylene-oxy-alkylene, arylene and
arylene --(CH.sub.2).sub.y --(Q).sub.n --(CH.sub.2).sub.y -arylene,
wherein each arylene radical is the same as Ar defined above;
wherein each y individually has a value of 0 to 1; wherein each Q
individually represents a divalent bridging group selected from the
class consisting of --CR.sup.1 R.sup.2 --, --O--, --S--, --NR.sup.3
--, --SiR.sup.4 R.sup.5 -- and --CO--, wherein each R.sup.1 and
R.sup.2 radical individually represents a radical selected from the
group consisting of hydrogen, alkyl of 1 to 12 carbon atoms,
phenyl, tolyl and anisyl, wherein each R.sup.3, R.sup.4 and R.sup.5
radical individually represents --H or --CH.sub.3 ; wherein each n
individually has a value of 0 to 1; and wherein m has a value of 2
to 6. Preferably each R.sup.1 and R.sup.2 individually represents
--H or CH.sub.3 ; and
F. phosphite compounds having the formula:
wherein R.sup.1 and R.sup.2 are aromatic groups which may be the
same or different, at least one of which aromatic groups group has
a pendants hindering group on a carbon atom adjacent to a carbon
atom bonded to the oxygen atom; A.sup.1 is an n-valent organic
group having an aliphatic hydrocarbon group, a cycloaliphatic
hydrocarbon group or an aromatic hydrocarbon group bonded with an
adjacent oxygen atom, which may respectively have a substituent; n
is an integer of from 2 to 4; and the respective
group may be the same or different.
Illustrative of the groups represented by the R groups in the above
formulas (I) to (VI) above include aryl, alkaryl, aralkyl, alkyl,
cycloalkyl, alkoxyaryl, hydroxyaryl, alkoxy-alkyl, and hydroxyalkyl
radicals. Representative R groups include phenyl, naphthyl,
o-tolyl, 2-ethylphenyl, 2,6-dimethylphenyl, 4-t-butylphenyl,
4-iso-pentylphenyl, nonylphenyl, benzyl, 2-phenylethyl,
4-phenylbutyl, methyl, ethyl, n-propyl, iso-propyl, n-butyl,
sec-butyl, t-octyl, n-decyl, iso-decyl, n-dodecyl, cyclohexyl,
cyclopentyl, 4-methylcyclohexyl, p-methoxyphenyl, p-hydroxyphenyl,
2-ethoxyethyl, 2-hydroxyethyl, and the like.
In formulas (I) to (VI) above, the symbols can have the same or
different meanings each time they occur (provided the meanings are
within the above definitions).
Specific illustrative examples of the phosphite ligands employable
in this invention within the scope of generic formulas (I) to (VI)
above include such preferred ligands as:
Examples of generic formula (I): ##STR7## Examples of generic
formula (II): ##STR8## Examples of generic formulas (III) and (IV):
##STR9## Examples of generic formula (V): ##STR10## Examples of
generic formula (VI): ##STR11##
In the practice of the present invention, the Group VIII metal
stabilizers are conveniently added to the hydroformylation in the
form of stabilizer precursors. The Group VIII compounds used as
phosphite stabilizer precursors in the process of the present
invention include the Group VIII metal carbonyl acetylacetonates,
oxides, acetylacetonates, carbonyls and nitrates. Preferred
phosphite stabilizers are compounds of ruthenium, cobalt, palladium
and platinum. In addition to containing the Group VIII metal, it is
important that the stabilizer precursor compound is soluble in the
hydroformylation reaction mixture and is free of rhodium catalyst
poisons such as cyanides, halides and sulfur compounds. Rhodium
compounds are useful as catalysts and/or catalyst precursors in the
present invention, but are not useful as stabilizers. On the
contrary, rhodium compounds catalyze degradation of the
phosphites.
The amounts of the starting materials employed in the process of
the present invention is not narrowly critical. Typically, the
amount of the Group VIII compound used as a stabilizer precursor is
the amount that provides up to a 10 molar excess of the Group VIII
metal based on the rhodium in the hydroformylation reaction
mixture. More usually, the amount of the Group VIII compound used
as a stabilizer precursor is the amount that provides from 1 to 5
moles of the Group VIII metal per mole of rhodium in the
hydroformylation reaction mixture. Typically, the amount of
phosphite ligand in the hydroformylation reaction mixtures used in
the process of the present invention is between about 0.005 and 15
weight percent based on the total weight of the reaction mixture.
More usually, the ligand concentration is between 0.001 and 10
weight percent, and most often is between about 0.05 and 5 weight
percent on that basis. Typically, the amount of rhodium in the
hydroformylation reaction mixtures used in the process of the
present invention is from 10 to 1000 parts per million by weight
based on the weight of the reaction mixture, more typically the
amount is between about 10 and 750 parts per million by weight
based on the weight of the reaction mixture and most typically the
amount is between about 20 and 500 parts per million by weight
based on the total weight of the reaction mixture.
In the process of the present invention, the metal stabilizer
precursor is added to and thoroughly mixed into the
hydroformylation reaction mixture using any convenient procedure.
The metal stabilizer precursor can be mixed with or dissolved in
any of the reactants or solvent and added to the hydroformylation
reaction mixture admixed with those materials or the precursor can
be separately added to the reactant mixture. The metal stabilizer
precursor can be added hydroformylation reaction mixture in small
quantities over an extended period during the hydroformylation
process. In this way, a concentration of metal stabilizer effective
to stabilize the ligand during steady-state operation is maintained
during the process. The metal stabilizer precursor also can be
added initially to the hydroformylation reaction mixture at a
higher than necessary concentration to achieve a long-term
stabilization by allowing the concentration to fall to lower, but
still effective, concentrations during the process without further
addition of stabilizer. The stabilizer precursor is converted in
the hydroformylation reaction mixture to an active complex
comprising the stabilizing metal in complex combination with carbon
monoxide and the above-described phosphite ligands. The complex may
also contain other ligands (e.g., the hydrogen and the olefin
reactant).
The hydroformylation reaction conditions that may be employed in
the process of the present invention generally include the
conditions heretofore disclosed in the art for hydroformylation
using catalysts comprising rhodium and phosphite ligands. For
instance, the total gas pressure of hydrogen carbon monoxide and
olefinic unsaturated starting compound of the hydroformylation
process may range from about 1 to about 10,000 psia (pound per
square inch absolute). In general, however, it is preferred that
the process be operated at a total gas pressure of hydrogen, carbon
monoxide and olefinic compound of less that about 1500 psia and
more preferably less than about 500 psia. The minimum total
pressure being limited predominately by the amount of reactants
necessary to obtain a desired rate of reaction. More specifically,
the carbon monoxide partial pressure is preferably from about 1 to
about 120 psia and, more preferably, from about 3 to about 90 psia,
while the hydrogen partial pressure is preferably about 15 to about
160 psia and, more preferably, from about 30 to about 100 psia. In
general H.sub.2 :CO molar ratio of gaseous hydrogen to carbon
monoxide may range from about 1:10 to 100:1 or higher, the more
preferred hydrogen to carbon monoxide molar ratio being from about
1:1 to about 10:1. Further, the hydroformylation process may be
conducted at a reaction temperature from about 45.degree. C. to
about 150.degree.. In general, hydroformylation reaction
temperature of about 50.degree. C. to about 120.degree. are
preferred for all types of olefinic starting materials. The more
preferred reaction temperatures are from about 50.degree. C. to
about 100.degree. C.
The olefinic compounds used as starting materials in the
hydroformylation process of the present invention include olefinic
compounds containing from 2 to 30 carbon atoms. Such olefinic
compounds can be terminally or internally unsaturated and be of
straight-chain, branched chain or cyclic structures such as
obtained from the oligomerization of propene, butene and isobutene
as well as dimeric, trimeric or tetrameric propylene and the like
disclosed in U.S. Pat. Nos. 4,518,809 and 4,528,403. Moreover,
mixtures of two or more different olefinic compounds may be
employed as the starting hydroformylation material if desired.
Further, such olefinic compounds and the corresponding aldehyde
products derived therefrom may also contain one or more groups or
substituents which do not unduly adversely affect the
hydroformylation process or the process of this invention such as
described, e.g., in U.S. Pat. Nos. 3,527,809 and 4,668,651.
Illustrative olefinic compounds are alpha-olefins, internal
olefins, alkyl alkenoates, alkenyl alkanoates, alkenyl alkyl
ethers, alkenols, and the like, e.g., ethylene, propylene,
1-butene, 1-pentene, 1-hexene, 1-octene, 1-nonene, 1-decene,
1-undecene, 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene,
1-hexadecene,1-heptadecene, 1-octadecene, 1-nonadecene, 1-eicosene,
2-butene, 2-methyl propene (isobutylene), 2-methylbutene,
2-pentene, 2-hexene, 3-hexane, 2-heptene, cyclohexene, propylene
dimers, propylene trimers, propylene tetramers, 2-ethyl-1-hexene,
2-octene, styrene, 3-phenyl-1-propene, 3-cyclohexyl-1-butene, allyl
alcohol, allyl butyrate, hex-1-en-4-ol, oct-1-en-4-ol, vinyl
acetate, allyl acetate, 3-butenyl acetate, vinyl propionate, allyl
propionate, methyl methacrylate, vinyl ethyl ether, vinyl methyl
ether, allyl ethyl ether, methyl-3-pentenoate,
n-propyl-7-octenoate, 3-butenenitrile, 5-hexenamide, 4-methyl
styrene, 4-isopropyl styrene, 4-tert-butyl styrene, alpha-methyl
styrene, 4-tert-butyl-alpha-methyl styrene,
1,3-diisopropenyl-benzene, eugenol, iso-eugenol, safrole,
iso-safrole, anethol, 4-allylanisole, indene, limonene, beta-pinene
and the like.
Mixtures of different olefinic compounds can be used as starting
materials in the hydroformylation process of the present invention.
The present invention is especially useful for the production of
aldehydes by hydroformylating alpha mono-olefinic hydrocarbons
containing from 2 to 20 carbon atoms and internal olefinic
hydrocarbons containing from 4 to 20 carbon atoms as well as
mixtures of such alpha-olefins and internal olefins.
Commercial-alpha-mono-olefins containing four or more carbon atoms
may contain minor amounts of corresponding internal mono-olefins
and/or their corresponding saturated hydrocarbon and that such
commercial mono olefins need not necessarily be purified from same
prior to being hydroformylated.
The hydroformylation process of the present invention can be
conducted in the presence of an organic solvent for the
rhodium-phosphite catalyst and any free phosphite ligand that might
be present. Any suitable solvent which does not unduly adversely
interfere with the intended hydroformylation reaction can be
employed. Suitable solvents for rhodium-catalyzed hydroformylation
processes include those disclosed in U.S. Pat. No. 4,668,651 and
also include saturated hydrocarbons, aromatic hydrocarbons, ethers,
aldehydes, ketones, nitriles and aldehyde condensation products.
Illustrative solvents include tetraglyme, pentanes, cyclohexane,
benzene, xylene, toluene, diethyl ether, butyraldehyde,
valeraldehyde, acetophenone, cyclohexanone, benzonitrile and
Texanol.RTM. (2,4,4,-trimethyl-1,3-pentanediol monoisobutyrate sold
by Eastman Kodak Company). Mixtures of one or more different
solvents may be employed if desired. Most preferably, the solvent
is a liquid organic compound in which the olefinic starting
material, catalyst and ligand are all substantially soluble. In
general, it is preferred to employ aldehyde compounds corresponding
to the aldehyde products desired to be produced and/or higher
boiling aldehyde liquid condensation by-products as the primary
solvent, such as the higher boiling aldehyde liquid condensation
by-products that are produced in situ during the hydroformylation
process. Indeed, while one may employ any suitable solvent at the
start up of a continuous process, the primary solvent in such a
process will normally eventually comprise both aldehyde products
and higher boiling aldehyde liquid condensation by-products due to
the nature of such continuous processes. Such aldehyde condensation
by-products can also be preformed and used from the start of the
process. The amount of solvent employed is not critical to the
present invention and need only be that amount sufficient to
provide the reaction medium with the particular rhodium
concentration desired for a given process. In general, the amount
of solvent may range from about 5 percent by weight up to about 95
percent by weight or more based on the total weight of the reaction
mixture.
The hydroformylation process of this invention can be conducted
using any suitable procedure, e.g., the liquid recycle procedure.
Such liquid catalyst recycle procedures are known as seen
disclosed, e.g., in U.S. Pat. Nos. 4,668,651; 4,774,361; 5,102,505
and 5,110,990. For instance, in such liquid catalyst recycle
procedures, it is commonplace to continuously remove a portion of
the liquid reaction product medium, containing, e.g., the aldehyde
product, the solubilized rhodium-phosphite catalyst, free phosphite
ligand and organic solvent, as well as by-products produced in situ
by the hydroformylation (e.g., aldehyde condensation by-products
etc.) and unreacted mono-olefinic starting material, carbon
monoxide and hydrogen (syn gas) dissolved in said medium from the
hydroformylation reactor, to a distillation zone (e.g., a
vaporizer/separator) wherein the desired aldehyde product is
distilled in one or more stages under normal, reduced or elevated
pressure, as appropriate, and separated from the liquid medium. The
vaporized or distilled desired aldehyde product so separated may
then be condensed and recovered in any conventional manner. The
remaining non-volatilized liquid residue which contains
rhodium-phosphite complex catalyst, solvent, free phosphite ligand
and usually some undistilled aldehyde product is then recycled
back, with or without further treatment as desired, along with
whatever by-product and non-volatilized gaseous reactants that
might still also be dissolved in said recycled liquid residue, in
any conventional manner desired, to the hydroformylation reactor.
Moreover, the reactant gases so removed by such distillation from
the vaporizer may also be recycled back to the reactor if
desired.
After the hydroformylation process of the present invention is
conducted, separation of the desired aldehyde product from the
crude reaction product may take place in any suitable manner.
Separation is usually accomplished by distillation at relatively
low temperatures, such as below 150.degree. C., and more preferably
at a temperature in the range of from about 50.degree. C. to about
130.degree. C. It is also preferred that such aldehyde distillation
take place under reduced pressure e.g., a total gas pressure that
is substantially lower than the total gas pressure employed during
hydroformylation when low boiling aldehydes (e.g., C.sub.4 to
C.sub.6 aldehydes) are involved or under vacuum when high boiling
aldehydes (e.g., C.sub.7 aldehydes or higher aldehydes) are
involved. For instance, the crude reaction product of the
hydroformylation process is subjected to a pressure reduction so as
to volatilize a substantial portion of the unreacted gases
dissolved in the product, the liquid product (which now contains a
much lower synthesis gas concentration than was present in the
crude reaction product) to the distillation zone where the desired
aldehyde product is distilled. In general, distillation pressures
ranging from vacuum pressures or below on up to total gas pressure
of about 50 psig should be sufficient for most purposes.
Infrared examination of a crude hydroformylation reaction product
containing phosphite-modified rhodium catalyst which does not
contain another Group VIII metal (such as a ruthenium compound) as
a phosphite stabilizer shows that some of the rhodium catalyst has
formed the rhodium cluster having a formula: Rh.sub.6 (CO).sub.16.
When ruthenium has been used as a stabilizer, either no Rh.sub.6
(CO).sub.16 is seen, or the quantities of that cluster are reduced.
Without wishing to be bound by any particular theory, it is
believed and that either Rh.sub.6 (CO).sub.16 or other rhodium
aggregate complexes which exist with Rh.sub.6 (CO).sub.16 (or
intermediates leading to such complexes) are responsible for
catalyzing the decomposition of phosphite ligands and that
ruthenium (or other Group VIII metal) reduces the concentration of
these complexes present in the hydroformylation reaction mixture.
In any event, it has been found that by reducing the concentrations
of these rhodium aggregates through addition of Group VIII metal
such as ruthenium, the extent of rhodium-catalyzed degradation of
the phosphite ligand is reduced.
In addition to reducing the degradation of phosphites as described
above, some Group VIII metals (particularly ruthenium, platinum,
cobalt and osmium) also reduce the extent of undesired
precipitation of rhodium from rhodium/phosphite-catalyzed
hydroformylation reaction mixtures (see Examples 9 to 14 below).
Such precipitation of rhodium decreases the amount of active
rhodium hydroformylation catalyst.
In the Examples appearing below, the abbreviations used have the
following meanings:
______________________________________ mL milliliters .degree. C.
degrees centigrade ppmw or ppm parts per million by weight wt. %
weight percent g mol/L/hr gram moles per liter per hour N/I moles
of normal butyraldehyde per mole of isobutyraldehyde in the
reaction product Ligand I Formula and name given below Ligand II
Formula and name given below acac acetylacetonate
______________________________________
The following Examples illustrate the present invention.
EXAMPLES 1 TO 8
Eight experiments (Examples 1 to 8) were conducted involving the
hydroformylation of propylene with hydrogen and carbon monoxide
using rhodium carbonyl acetylacetonate as the catalyst precursor,
"Ligand I" or "Ligand II" as the phosphite ligand and tetraglyme as
the solvent. The formula and name of Ligands I and II are as
follows: ##STR12## The experiments were conducted with and without
a transition metal stabilizer and the composition of the reaction
mixtures used in the experiments are shown in Table 1. The
experiments were conducted as follows:
The hydroformylation reactions were conducted in a glass pressure
reactor operating in a continuous mode. The reactor consisted of a
three-ounce pressure bottle partially submersed in an oil bath with
a glass front for viewing. After purging the system with nitrogen,
about 20-mL of a freshly prepared rhodium catalyst precursor
solution was charged to the reactor with a syringe. The catalyst
precursor solution contained about 250 ppm rhodium (introduced as
rhodium dicarbonyl acetylacetonate), metal stabilizer precursor
(where used), ligand and tetraglyme as solvent. After sealing the
reactor, the system was again purged with nitrogen, and the oil
bath was heated to furnish the desired hydroformylation reaction
temperature. The hydroformylation reaction was conducted at a total
gas pressure of about 160 psig and 100.degree. C. reaction
temperature. The partial pressures of hydrogen, carbon monoxide,
and propylene during the reaction are given in Tables 2 to 7 below.
The remainder of the pressure of the reaction mixture is from the
partial pressures of nitrogen and aldehyde product. The flows of
the feed gases (carbon monoxide, hydrogen, propylene and nitrogen)
were controlled individually with mass flow meters and the feed
gases were dispersed in the catalyst precursor solution via fritted
metal spargers. The unreacted portion of the feed gases was
stripped out the butyraldehydes produced in the reaction. The
outlet gas was analyzed over the indicated number of days of
continuous operation. The analytical results for Examples 1 to 6
are given in Tables 2 to 7 below. The average reaction rates for
Examples 1 to 6 (in terms of gram moles per liter per hour of the
butyraldehyde products) as well as the n-butyraldehyde to
iso-butyraldehyde product ratio (N/I) for those Examples that are
also given in Tables 2 to 7 below.
TABLE 1 ______________________________________ Composition of
Reaction Mixtures Used in Examples 1-8 to Determine the Effect of
Added Metal Stabilizers on Ligand Stabilization. Dodeca- Tetra-
Rh(CO).sub.2 acac phenone Ex- glyme Ligands I Catalyst ***
Stabilizer/ ample grams grams grams grams Grams
______________________________________ 1. 29.5 0.405* 0.0189 0.30
None 2. 29.5 0.405* 0.0191 0.30 Ru.sub.3 (CO).sub.12 / 0.0316 3.
29.5 0.405* 0.0189 0.30 Co.sub.2 (CO).sub.8 / 0.0249 4. 29.5 0.405*
0.019 0.30 Pt(acac)2/ 0.0573 5. 29.5 0.405* 0.0189 0.30
Pd(acac).sub.2 / 0.0448 6. 29.5 0.405* 0.0188 0.30 Os.sub.3
(CO).sub.12 / 0.0442 7. 28.2 1.2** 0.0152 0.30 None 8. 28.2 1.2**
0.0152 0.30 Co.sub.2 (CO).sub.8 / 0.0199
______________________________________ *Ligand I was used in the
experiment **Ligand II was used in the experiment ***Internal
standard for liquid chromatography.
TABLE 2 ______________________________________ Example 1. Control.
Ligand I, no Stabilizer Reaction Rate Test Results - Daily Averages
Partial Pressure psi Rate N/I Days CO H2 C3H6 gmol/L/hr Ratio
______________________________________ 0.6 53.1 46.4 13.3 2.050 0.8
1.5 51.3 47.4 16.5 1.732 0.7 2.5 51.9 46.8 16.9 1.530 0.7 3.6 52.1
46.8 17.1 1.458 0.7 4.5 52.4 46.8 17.2 1.508 0.8 5.5 52.5 47.1 17.7
1.427 0.8 6.5 52.2 47.0 18.0 1.471 0.8 7.5 51.6 46.7 18.0 1.433 0.8
8.4 51.3 46.6 18.5 1.462 0.8 9.4 50.9 46.3 18.7 1.491 0.8 10.1 50.8
46.5 18.3 1.454 0.7 11.1 50.6 46.1 19.1 1.370 0.7 12.4 50.5 46.1
19.7 1.428 0.8 13.5 51.9 45.2 20.0 1.422 0.8 14.5 52.4 45.0 20.6
1.409 0.8 ______________________________________
TABLE 3 ______________________________________ Example 2. Ligand I,
Ruthenium Stabilizer Reaction Rate Test Results - Daily Averages
Partial Pressure psi Rate N/I Days CO H2 C3H6 gmol/L/hr Ratio
______________________________________ 0.5 51.4 47.2 21.9 1.376 0.8
1.5 49.0 46.0 27.0 1.063 0.7 2.4 48.6 45.1 31.2 1.011 0.7 3.5 48.5
45.0 32.2 0.954 0.7 4.5 48.3 45.0 32.9 0.950 0.7 5.4 48.7 45.0 33.4
0.948 0.7 6.5 49.3 45.6 32.3 0.976 0.7 7.5 49.5 44.5 32.8 1.024 0.7
8.4 49.9 45.0 31.6 1.014 0.7 9.4 49.3 44.6 34.8 1.039 0.7 10.1 49.2
44.1 35.0 1.085 0.7 11.1 49.2 44.2 35.1 1.129 0.7 12.4 48.9 44.5
35.5 1.103 0.7 13.5 49.3 45.2 35.3 1.163 0.7 14.5 49.7 45.6 35.1
1.179 0.7 ______________________________________
TABLE 4 ______________________________________ Example 3. Ligand I,
Cobalt Stabilizer Reaction Rate Test Results - Daily Averages
Partial Pressure psi Rate N/I Days CO H2 C3H6 gmol/L/hr Ratio
______________________________________ 0.5 50.7 50.0 25.3 0.321 0.9
1.4 49.4 47.4 26.1 0.616 0.8 2.5 47.5 46.5 26.2 0.831 0.8 3.2 46.9
46.2 26.4 0.888 0.8 4.2 47.1 46.1 26.4 0.929 0.9 5.5 47.3 45.6 26.4
0.915 1.0 6.6 47.8 44.9 26.7 0.933 1.0 7.6 48.1 44.8 26.7 0.950 1.0
8.6 48.0 44.8 26.5 0.957 0.9 9.5 48.0 44.9 26.8 1.060 0.9 10.6 48.1
44.7 26.6 1.134 0.9 11.6 47.4 44.4 26.0 1.231 0.8 12.6 47.4 44.5
25.7 1.358 0.8 13.6 47.3 44.7 25.3 1.472 0.8
______________________________________
TABLE 5 ______________________________________ Example 4. Ligand I,
Platinum Stabilizer Reaction Rate Test Results - Daily Averages
Partial Pressure psi Rate N/I Days CO H2 C3H6 gmol/L/hr Ratio
______________________________________ 0.5 51.1 47.5 9.8 1.275 0.8
1.4 52.1 48.3 12.4 0.999 0.8 2.5 52.1 48.5 13.7 0.922 0.8 3.2 52.0
48.0 14.0 0.944 0.8 4.2 49.7 46.6 13.7 0.865 0.8 5.5 51.1 48.2 14.3
0.871 0.8 6.6 52.8 47.4 15.2 0.847 0.8 7.6 53.1 47.0 15.8 0.846 0.8
8.6 53.3 46.3 15.8 0.846 0.8 9.6 52.5 46.3 17.7 0.959 0.8 10.6 52.3
46.4 18.0 0.927 0.8 11.6 52.2 46.5 18.0 0.912 0.8 12.6 51.6 46.4
18.5 0.918 0.8 13.6 51.6 46.0 19.2 0.955 0.8
______________________________________
TABLE 6 ______________________________________ Example 5. Ligand I,
Palladium Stabilizer Reaction Rate Test Results - Daily Averages
Partial Pressure psi Rate N/I Days CO H2 C3H6 gmol/L/hr Ratio
______________________________________ 0.5 51.5 47.2 10.1 1.246 0.7
1.4 51.5 46.1 11.2 1.188 0.8 2.5 51.5 45.6 12.4 1.175 0.8 3.2 51.4
45.7 12.5 1.198 0.8 4.2 51.2 45.6 12.7 1.280 0.8 5.5 51.2 45.2 13.2
1.233 0.8 6.6 51.4 45.2 14.0 1.213 0.8 7.6 51.8 45.3 14.3 1.218 0.8
8.5 51.5 44.5 14.4 1.203 0.8 9.6 52.1 44.4 15.0 1.230 0.8 10.6 52.5
44.4 15.3 1.181 0.8 11.6 52.3 44.7 15.2 1.146 0.8 12.5 51.1 45.2
15.2 1.166 0.8 13.6 51.1 44.3 15.8 1.175 0.8
______________________________________
TABLE 7 ______________________________________ Example 6. Ligand I,
Osmium Stabilizer Reaction Rate Test Results - Daily Averages
Partial Pressure psi Rate N/I Days CO H2 C3H6 gmol/L/hr Ratio
______________________________________ 0.5 51.0 47.1 10.1 1.275 1.0
1.4 51.2 46.7 10.6 1.449 0.8 2.5 50.9 46.8 11.2 1.369 0.8 3.2 50.8
46.5 11.4 1.379 0.8 4.2 50.5 46.3 11.6 1.410 0.8 5.5 50.6 46.8 12.4
1.395 0.8 6.6 51.7 46.0 13.1 1.337 0.8 7.6 52.2 46.0 13.7 1.283 0.8
8.6 52.3 45.9 14.5 1.240 0.8 9.5 51.7 45.6 15.6 1.260 0.8 10.6 51.9
46.1 16.0 1.204 0.8 11.5 51.5 46.2 16.0 1.181 0.8 12.5 51.5 46.0
17.3 1.182 0.8 13.5 51.5 46.0 17.3 1.182 0.8
______________________________________
The Ligand I concentrations in the hydroformylation reaction
mixtures during Examples 1-6 was monitored by High Performance
Liquid Chromatography of catalyst samples removed from each reactor
periodically. The results of these analyses are presented below in
Tables 8, 9, 10. The data in Table 8 (presented as percent Ligand I
remaining with time) show that one half of the Ligand I in the
control experiment (no added metal stabilizer) decomposed in 12 to
15 days of continuous hydroformylation whereas similar reaction
mixtures containing cobalt or platinum as stabilizers show very
little Ligand I decomposition.
TABLE 8 ______________________________________ Ligand I
Decomposition Rates in the Presence and Absence of Transition Metal
Stabilizers: Comparative Experiments with and without added Cobalt
or Platinum. Example 1 Days of Rh/Ligand I Example 3 Example 4
Operation (Control) Rh/Co/Ligand I Rh/Pt/Ligand I
______________________________________ Percent Ligand I Remaining 1
100 100 100 5 72 104 92 8 66 97 96 12 53 103 94 15 49 -- --
______________________________________
Similarly, ruthenium and palladium were also found to stabilize
Ligand I (see Table 9 below).
TABLE 9 ______________________________________ Ligand I
Decomposition Rates in the Presence and Absence of Transition Metal
Stabilizers: Comparative Experiments with and without added
Palladium or Ruthenium. Example 1 Days of Rh/Ligand I Example 5
Example 2 Operation (Control) Rh/Pd/Ligand I Rh/Ru/Ligand I
______________________________________ Percent Ligand I Remaining 1
100 100 96 5 72 87 75 8 66 82 73 12 53 78 67 15 49 -- 64
______________________________________
Unlike the other metals tested above, osmium showed very small
stabilizing effect (Table 10).
TABLE 10 ______________________________________ Ligand I
Decomposition Rates in the Presence and Absence of Transition Metal
Stabilizers: Comparative Experiments with and without added Osmium
Example 1 Days of Rh/Ligand I Example 6 Operation (Control)
Rh/Os/Ligand I ______________________________________ Percent
Ligand I Remaining 1 100 91 5 72 79 8 66 69 12 53 59 15 49 --
______________________________________
The results shown in Tables 8, 9 and 10 above lead to the following
conclusions: Under conditions which cause significant Ligand I
decomposition in continuous propylene hydroformylation in Examples
1, the extent of Ligand I decomposition is significantly lowered
when cobalt, platinum, ruthenium or palladium are used as
stabilizers.
The compositions of the hydroformylation reaction mixtures used in
Examples 7 and 8 are given above in Table 1. Example 7 was the
control (no added stabilizer) and Example 8 employed added cobalt
as stabilizer. The average reaction rates for Examples 7 and 8 (in
terms of gram moles per liter per hour of the butyraldehyde
products) as well as the n-butyraldehyde to iso-butyraldehyde
product ratio (N/I) are given in Tables 11 and 12 below.
TABLE 11 ______________________________________ Example 7. Ligand
II, Control (no stabilizer added) Reaction Rate Test Results -
Daily Averages Days of Partial Pressure (psia) Rate N/I Operation
CO H2 C3H6 gmol/L/hr Ratio ______________________________________
0.6 53.1 46.4 13.3 2.050 0.8 1.5 51.3 47.4 16.5 1.732 0.7
______________________________________
TABLE 12 ______________________________________ Example 8. Ligand
II, Cobalt stabilizer Reaction Rate Test Results - Daily Averages
Days of Partial Pressures (psia) Rate N/I Operation CO H2 C3H6
gmol/L/hr Ratio ______________________________________ 0.5 47.8
47.5 11.3 0.975 1.0 1.4 52.4 46.2 14.5 0.628 1.5
______________________________________
Analysis of the crude reaction products by Phosphorus-31 Nuclear
Magnetic Resonance (P-31 NMR) spectroscopy showed that Ligand II in
control Example 7 (no added metal stabilizer) had undergone over
50% decomposition to several phosphorus-containing byproducts
whereas the reaction mixture containing the cobalt stabilizer
(Example 8) showed no decomposition byproducts in the P-31 NMR
spectrum.
EXAMPLES 9 TO 14
Examples 9 and 14 below illustrate the stabilization of rhodium in
hydroformylation reaction mixtures containing rhodium/phosphite
complex catalysts using various transition metal stabilizers. The
crude hydroformylation reaction products produced in the continuous
hydroformylation tests described in Examples 1 to 6 above were
subjected to a rhodium loss test to determine the effect of the
Group VIII metal that had been added to stabilize the phosphite in
also stabilizing rhodium against precipitation as insoluble
complexes or as metallic rhodium. This rhodium loss test simulates
harsh hydroformylation reaction conditions in order to accelerate
and magnify the rhodium loss phenomenon and to allow meaningful
measurements within a shorter time frame. For this test, each crude
reaction product was first analyzed for rhodium by Atomic
Absorption Spectroscopy (AA) and was then heated in a
Fischer-Porter pressure bottle at 130.degree. C. under 10 psig
hydrogen for 20 hours. The resulting solution was filtered through
a 0.5 micron filter to remove any insoluble complexes and analyzed
by AA to determine the concentration of the remaining soluble
rhodium. The rhodium concentration before and after these
experiments is given in Table 13.
TABLE 13 ______________________________________ Rhodium Loss Test
Result Using Rhodium Ligand I Catalyst and Transition Metal
Stabilizers. Soluble RH Rh Before Test Rh After Test Remaining
Example Stabilizer ppm ppm Percent
______________________________________ 9 None 229 56 25 10
Ruthenium 245 212 87 11 Platinum 205 143 70 12 Cobalt 219 102 46 13
Osmium 184 73 40 14 Palladium 195 36 18
______________________________________
The results in Table 13 show that (except for palladium) the metal
stabilizes the rhodium.
EXAMPLE 15
The purpose of this Example was to determine whether daily
additions of dodecane epoxide to a hydroformylation reaction
mixture containing a rhodium/Ligand I complex catalyst stabilizes
ring hydroformylation relative to a control containing no epoxide.
Dodecane epoxide is disclosed in above-mentioned published European
patent Application 0590611 as a stabilizer to reduce the
acid-catalyzed hydrolytic degradation of phosphites. A
rhodium/ruthenium/Ligand I complex catalyst was also tested
simultaneously to compare its performance under identical
hydroformylation conditions.
In this Example, three glass pressure reactors were used as
described in Example 1 above. The composition of the reaction
mixture for the epoxide-addition experiment and the control
experiment (no epoxide and no metal stabilizer) is shown in Table 1
(see Example 1 in Table 1). The composition of the reaction mixture
for the experiment involving the rhodium/ruthenium/Ligand I
catalyst is shown in Table 1 (see Example 2 in Table 1). The
experimental conditions and reaction rate data from the three tests
are shown in Tables 14 to 17 below.
TABLE 14 ______________________________________ Control. Rh/Ligand
I Catalyst Reaction Rate Test Results - Daily Averages Days Partial
Pressures, psi Rate Operation CO H2 C3H6 gmol/L/hr N/I
______________________________________ 0.8 41.7 41.2 19.1 0.936 0.7
1.5 41.6 40.6 7.7 1.086 0.7 2.5 43.1 41.6 3.8 1.844 0.8 3.4 44.8
43.0 3.3 0.966 0.8 4.5 45.4 43.4 2.4 1.530 0.9 5.4 45.5 43.4 2.6
1.514 0.8 6.5 45.5 44.2 2.5 1.544 0.9 7.5 45.3 43.8 2.6 1.531 0.9
8.5 45.8 44.1 2.7 1.583 0.9 9.5 45.0 43.6 3.2 1.705 0.9 10.5 45.6
44.2 2.8 1.687 0.9 11.1 45.7 44.5 2.9 1.879 2.3 12.2 45.8 44.1 3.1
1.557 0.9 ______________________________________
TABLE 15 ______________________________________ Epoxide added daily
to a Rh/Ligand I Catalyst Reaction Rate Test Results - Daily
Averages Days Partial Pressures, psi Rate Operation CO H2 C3H6
gmol/L/hr N/I ______________________________________ Target 45.0
45.0 10.0 2.000 0.0 0.5 43.3 40.3 28.7 1.652 0.7 1.5 38.9 37.5 16.0
2.127 0.7 2.5 40.2 37.9 15.9 2.135 0.7 3.5 40.9 37.9 15.8 2.122 0.7
4.5 41.2 39.1 14.6 2.089 0.7 5.5 40.8 38.9 15.8 2.072 0.7 6.4 41.0
38.7 16.3 3.912 0.7 7.5 41.0 38.6 17.1 1.991 0.7 8.5 41.8 40.3 16.4
2.023 0.7 9.5 41.7 40.2 17.5 2.024 0.7 10.4 42.5 41.5 16.5 1.856
0.8 11.5 42.4 41.0 17.8 1.971 0.7
______________________________________
TABLE 16 ______________________________________ Ruthenium
Stabilizer Comparison Reaction Rate Test Results - Daily Averages
Days Partial Pressures, psi Rate Operation CO H2 C3H6 gmol/L/hr N/I
______________________________________ Target 45.0 45.0 10.0 2.000
0.0 0.6 49.0 45.4 32.7 0.532 1.0 1.5 48.7 46.4 30.2 0.701 0.9 2.5
47.2 45.6 31.3 0.862 0.9 3.5 46.8 45.0 31.1 1.017 0.8 4.5 46.3 44.7
30.9 1.195 0.8 5.6 45.8 44.4 30.6 1.383 0.8 6.5 46.1 44.5 29.3
1.468 0.8 7.5 45.1 43.3 31.9 1.477 0.8 8.5 45.4 44.1 30.5 1.306 0.8
9.5 46.1 44.1 28.7 1.354 0.8 10.4 45.9 44.4 28.6 2.525 0.8 11.4
45.0 43.7 30.9 1.426 0.8 ______________________________________
After about twelve days of continuous operation, crude
hydroformylation reaction products were withdrawn from each reactor
and analyzed by phosphorus-31 Nuclear Magnetic Resonance (NMR)
spectroscopy. Analysis of the NMR result shows that ligand
decomposition occurred in all three hydroformylation reactions but
the decomposition was lowest in the hydroformylation reaction with
ruthenium as stabilizer and highest in the hydroformylation
reaction to which 0.2 ml dodecane epoxide was added. These results
are shown in Table 17.
TABLE 17 ______________________________________ Ligand I Stability
Epoxide vs Ruthenium Comparison Ligand Stabilities as Determined by
Relative Areas of P-31 NMR Peaks Ligand Ligand Remaining
Decomposition Peak Products Ligand Counts Peak Counts Remaining
______________________________________ Control 5724 4103 58% (no
additives) Epoxide 1874 7048 21% (added daily) Ruthenium 4677 1608
74% additive ______________________________________
* * * * *